Adhesive composition

ABSTRACT

Provided is a two-part composition comprising 
     A) An epoxy terminated polyester having the structure 
     
       
         
         
             
             
         
       
         
         
           
             wherein R 1 — is 
           
         
       
    
     
       
         
         
             
             
         
       
         
         
           
             G- is 
           
         
       
    
     
       
         
         
             
             
         
       
         
         
           
             j is 0 to 5, —R 2 — is a divalent organic group, —R 22 — is a divalent alkyl group, and —R 22 — is a divalent alkyl group, and 
           
         
       
    
     B) one or more epoxy curing agent, each molecule of which comprises two or more active hydrogen atoms that are each capable of reacting with an epoxy group.

Epoxy-terminated compounds are useful for a variety of purposes. Forexample, epoxy-terminated compounds may undergo chemical reactionseither with themselves or with one or more co-reactant to form polymersthat have high molecular weight and/or are crosslinked. Such polymersare often useful for one or more of a wide variety of purposes, such as,for example, as adhesives.

US 2008/0081883 describes polyester polyols that are reaction productsof 2,5-furandicarboxylic acid and polyepoxides. It is desired to provideepoxy terminated compounds that react well with polyamines to formuseful adhesive compositions, such as, for example, laminatingadhesives. It is also desired to provide epoxy terminated compounds thathave desirably low viscosity over the temperature range of fromapproximately 25° C. to approximately 70° C.

The following is a statement of the invention.

The first aspect of the present invention is a two-part compositioncomprising

-   A) an epoxy terminated polyester having the structure

where R¹— is

G- is

j is 0 to 5, —R²— is a divalent organic group, —R²¹— is a divalent alkylgroup, and —R²²— is a divalent alkyl group, and

-   B) one or more epoxy curing agent, each molecule of which comprises    two or more active hydrogen atoms that are each capable of reacting    with an epoxy group.

The following is a detailed description of the invention.

As used herein, the following terms have the designated definitions,unless the context clearly indicates otherwise.

An epoxy terminated compound is a compound that contains one or morestructure I

A diepoxide is a compound having exactly two groups of structure I. Aglycidyl ether terminated compound is a compound that contains one ormore structure II

An ester linkage is the structure III

A polyester is a compound that has two or more ester linkages. A polyolis a compound that has two or more —OH groups. A diol is a compound thathas exactly two —OH groups. A polyamine is a compound that has two ormore amine groups; the amine groups may be primary or secondary or amixture thereof. A diamine is a compound that has exactly two aminegroups; a diamine may have two primary amine groups, two secondary aminegroups, or one primary amine group and one secondary amine group. Adicarboxylic acid is a compound having exactly two —COOH groups.

An aliphatic group is a chemical group that contains only carbon andhydrogen atoms and that contains no aromatic rings. A cycloaliphaticgroup is an aliphatic group that contains one or more cyclic structures.An alkyl group is an aliphatic group that has no double bonds. Alkylgroups include, for example, monovalent and divalent alkyl groups suchas, for example, methylene groups, methyl groups, ethylene groups, ethylgroups, and larger alkylene and alkyl groups. A cycloalkyl group is analkyl group that contains one or more cyclic structures. An aromaticgroup is any group having an aromatic ring.

An aliphatic amine is an amine in which the nitrogen atom of each aminegroup is bonded to a carbon atom that is part of an aliphatic group. Anaromatic amine is an amine in which the nitrogen atom of each aminegroup is bonded to a carbon atom that is part of an aromatic ring.

When a ratio is said herein to be X:1 or greater, it is meant that theratio is Y:1, where Y is greater than or equal to X. For example, if aratio is said to be 3:1 or greater, that ratio may be 3:1 or 5:1 or100:1 but may not be 2:1. Similarly, when ratio is said herein to be W:1or less, it is meant that the ratio is Z:1, where Z is less than orequal to W. For example, if a ratio is said to be 15:1 or less, thatratio may be 15:1 or 10:1 or 0.1:1 but may not be 20:1.

The composition of the present invention is an epoxy terminatedpolyester having structure IV

In structure IV, the two —R¹ groups may be identical or different. EachR¹ group has the structure V

The group —R²— is a divalent organic group having fewer than 50 carbonatoms. The group G- has the structure II defined herein above. Thenumber j is 0 to 5. The group —R²¹— is a divalent alkyl group. The group—R²²— is a divalent alkyl group.

The composition of the present invention may also contain, in additionto one or more compounds having structure IV, one or more compoundshaving structure IVA

where —B¹— has the structure

—B²— has the structure

-Q- has the structure

j is 0 to 5, and n is 1 to 6. The group —R²¹— is a divalent alkyl group.The group —R²²— is a divalent alkyl group.

Preferably, —R²— is a group having structure VI

The number p is 0 to 20. Preferably p is 0 to 10; more preferably 0 to5. Each —R³—, each —R⁴—, and each —R⁵— is, independent of the other, adivalent organic group. Within a single —R²— group, if p is 2 orgreater, the various —R³— groups may be identical to each other ordifferent from each other. Within a single —R²— group, if p is 2 orgreater, the various —R⁴— groups may be identical to each other ordifferent from each other.

Preferably, —R³— is selected from one or more divalent aliphatic groups,one or more divalent aromatic hydrocarbon groups, or a mixture thereof.Among aliphatic groups, preferred are alkyl groups; more preferred arelinear or branched alkyl groups; more preferred are linear alkyl groups.Among aliphatic groups, preferred are those with 1 or more carbon atoms;more preferred are those with 2 or more carbon atoms; more preferred arethose with 3 or more carbon atoms. Among aliphatic groups, preferred arethose with 12 or fewer carbon atoms; more preferred are those with 8 orfewer carbon atoms; more preferred are those with 6 or fewer carbonatoms. Among aliphatic groups, preferred is —CH₂CH₂CH₂CH₂—. Amongaromatic groups, preferred are those with the structure

including mixtures of isomers; more preferred is

The groups that are suitable and preferred for —R⁵— are the same asthose for —R³—. The group —R⁵— may be different from all of the —R³—groups, or —R⁵— may be the same as one or all of the —R³— groups.

Preferably, —R⁴— is either an aliphatic group or is an aliphatic ethergroup. An aliphatic ether group has the structure VII

where —R⁸— and —R⁹— (if present) and —R¹⁰— are aliphatic groups, andwhere r is 0 to 10. The groups —R⁸— and —R⁹— (if present) and —R¹⁰— maybe identical or may be different from each other. When —R⁴— is analiphatic ether group, the following preferences apply to —R⁸—, —R⁹— (ifpresent), —R¹⁰—, and r. Preferably, —R⁸— and —R⁹— (if present) and —R¹⁰—are identical. Preferably —R⁸— and —R⁹— (if present) and —R¹⁰— arelinear or branched alkyl groups. Preferably —R⁸— and —R⁹— (if present)and —R¹⁰— each have 4 or fewer carbon atoms; more preferably 3 or fewercarbon atoms; more preferably exactly 2 carbon atoms. Preferably, r is 0to 10; more preferably 0 to 5; more preferably 0 to 2; more preferablyzero. When —R⁴— is an aliphatic group, —R⁴— is preferably an alkylgroup; more preferably a linear alkyl group. When —R⁴— is an aliphaticgroup, —R⁴— has 1 or more carbon atom. When —R⁴— is an aliphatic group,—R⁴— preferably has 6 or fewer carbon atoms; more preferably 4 or fewercarbon atoms; more preferably 3 or fewer carbon atoms; more preferablyexactly 2 carbon atoms.

In some embodiments (herein called “mixed polyester” embodiments), p isgreater than 1, and some of the —R³— groups are not identical to other—R³— groups. In some mixed polyester embodiments, —R²— has the structureVIII

The groups —R³— and —R⁴— and —R⁵— are as defined herein above, and q is1 or higher. Preferably q is 0 to 9; more preferably 1 to 4. Thesuitable and preferable groups for —R⁶— are the same as those for —R⁴—.The suitable and preferable groups for —R⁷— are the same as those for—R³—. In some mixed polyester embodiments (herein called “MP1”embodiments), —R⁵— is identical to —R³—, —R⁶— is identical to —R⁴—, and—R⁷— is different from —R³—. In some MP1 embodiments, all the —R⁴—groups are identical to each other; in other MP1 embodiments, some —R⁴—groups are different from other —R⁴— groups. In some mixed polyesterembodiments (herein called “MP2” embodiments), —R⁵— is identical to—R⁷—, —R⁶— is identical to —R⁴—, and —R⁷— is different from —R³—. Insome MP2 embodiments, all the —R⁴— groups are identical to each other;in other MP2 embodiments, some —R⁴— groups are different from other —R⁴—groups.

Preferred embodiments are selected from the following:

-   -   (a) embodiments in which p=0;    -   (b) embodiments in which p is 1 or greater and in which all the        —R³— groups are identical to each other, all the —R⁴— groups are        identical to each other, and —R⁵— is identical to —R³—;    -   (c) MP1 embodiments; and    -   (d) MP2 embodiments;

In structure V, j is preferably 1 or more. In structure V, j ispreferably 5 or less; more preferably 4 or less; more preferably 3 orless; more preferably 2 or less. In structure V, j is most preferably 1.

In structure V, —R²¹— is a divalent alkyl group. Preferably, —R²¹— has 2or more carbon atoms; more preferably 3 or more carbon atoms.Preferably, —R²¹— has 6 or fewer carbon atoms; more preferably 5 orfewer carbon atoms; more preferably 4 or fewer carbon atoms. Mostpreferably, —R²¹— has 3 carbon atoms. Among embodiments in which —R²¹—has 3 carbon atoms, preferably —R²¹— is selected from structures XX,XXI, and XXII:

In some embodiments, a mixture of polyesters will be present in whichone polyester will have —R²¹— that is one of XX, XXI, or XXII, andanother polyester will be present in which —R²¹— is a different one ofXX, XXI, or XXII.

In structure V, if j is 1 or more, the suitable and preferred structuresfor —R²²— are the same as those for —R²¹—. The group —R²²— may be thesame as —R²¹— or different from —R²¹—. If j is 2 or more, each —R²²— maybe the same as every other —R²²— or some —R²²— groups may be differentfrom other —R²²— groups. Preferably, every —R²²— has the same number ofcarbon atoms as every other —R²²—. Preferably —R²¹— has the same numberof carbon atoms as every —R²²— group. Preferably, every —R²²— has threecarbon atoms. Preferably, at least one —R²²— has structure XXI or XXII.

The epoxide terminated polyesters of this invention will preferably havean Epoxide Equivalent Weight (EEW) of 275 or higher; more preferably 350or higher; more preferably 400 or higher. The epoxide terminatedpolyesters of this invention will preferably have an Epoxide EquivalentWeight (EEW) of 3500 or lower; more preferably 2500 or lower; morepreferably 2000 or lower. The number-average molecular weight of theepoxy terminated polyester of the present invention will preferably be500 or higher; more preferably 1000 or higher. The number-averagemolecular weight of the epoxy terminated polyester of the presentinvention will preferably be 8000 or lower, more preferably 6000 orlower, and more preferably 3500 or lower.

It is useful to characterize the level of low molecular weight (<1000Daltons) species present in the composition of the present invention.The level of low molecular weight species is defined as the percentageby weight of species having molecular weight of less than or equal to1000 Daltons, based on the total weight of the composition. The level oflow molecular weight species is preferably 55% or less; more preferably30% or less; more preferably 25% or less.

The composition of the present invention may be made by any method. Apreferred method includes reacting at least one diepoxide with at leastone dicarboxylic acid. The diepoxide has the structure IX

G-Q-G   IX

G- is defined as in structure V. Q is defined as in structure IVA. Thedicarboxylic acid has the structure X

The group —R²— is defined as in structure IV. Sufficient amount ofcompound having structure IX is used so that the reaction producescompound having structure IV.

Preferred compounds of structure X have acid value (which is measured asdescribed below) of 110 or higher; more preferably 120 or higher; morepreferably 125 or higher. Preferred compounds of structure X have acidvalue of 260 or lower; more preferably 200 or lower; more preferably 175or lower. Preferred compounds of structure X have molecular weight of430 or higher; more preferably 560 or higher; more preferably 640 orhigher. Preferred compounds of structure X have molecular weight of 1020or lower; more preferably 940 or lower; more preferably 900 or lower.Mixtures of suitable Mixtures of suitable compounds of structure X arealso suitable are also suitable.

In the reaction of at least one diepoxide with at least one dicarboxylicacid, the stoichiometric ratio of epoxide groups to carboxylic acidgroups will preferably be 3.1:1 or greater; more preferably 2.9:1 orgreater; more preferably 2.7:1 or greater. The stoichiometric ratio ofepoxide groups to carboxylic acid groups will preferably be 2:1 or less;more preferably 1.6:1 or less; more preferably 1.3:1 or less.

The reaction of diepoxide with dicarboxylic acid is optionally conductedin the presence of a catalyst. Preferred catalysts are triarylphosphorous compounds with a soluble chromium catalyst,tetra-substituted phosphonium salts, quaternary ammonium salts,carbonate salt, hydroxide salts, and salts of carboxylic acids. Morepreferred are tetra-substituted phosphonium salts, carbonate salts, andsalts of carboxylic acids.

When a triaryl phosphorous compound is used in combination with achromium compound, the preferred triaryl phosphorous compounds aretriaryl phosphines. Preferred triaryl phosphines are triphenyl phosphinetritolyl phosphine, trixylyl phosphine, and trinaphthyl phosphine. Whena triaryl phosphorous compound is used in combination with a chromiumcompound, the preferred the preferred chromium compounds are chromiumtriacetate and chromium trichloride. Among the tetra-substitutedphosphonium salts, preferred are alkyltriphenylphosphonium salts,tetraarylphosphonium salts, benzyltrialkylphosphonium salts, andtetraalkylphosphonium salts; more preferred arealkyltriphenylphosphonium salts and benzyltrialkylphosphonium salts.Among alkyltriphenylphosphonium salts, preferred areethyltriphenylphosphonium acetate/acetic acid complex, andethyltriphenlyphosphonium iodide; more preferred isethyltriphenylphosphonium iodide. Among tetraalkylphosphonium salts,preferred is tetrabutylphosphonium acetate/acetic acid complex. Amongbenzyltrialkyl phosphonium salts, preferred is benzyltrimethylphosphonium chloride. Among tetraarylphosphonium salts, preferred istetraphenylphosphonium bromide.

Among the quaternary ammonium salts, preferred arebenzyltrimethylammonium chloride, tetramethylammonium chloride, anddiphenyldimethylammonium chloride. Among the salts of carboxylic acids,preferred are sodium or potassium salts of mono-carboxylic acids; morepreferred are sodium acetate, potassium acetate, sodium propionate,potassium propionate, sodium benzoate, potassium benzoate, sodiumcitrate, potassium citrate, sodium lactate, potassium lactate, sodiumtartrate, potassium tartrate, and sodium potassium tartrate. Among theinorganic bases, preferred are sodium carbonate, potassium carbonate,sodium hydroxide, and potassium hydroxide.

The preferred catalysts for the preparation of epoxy terminatedpolyesters are ethyltriphenlyphosphonium iodide, benzyltrimethylammoniumchloride, sodium carbonate, and sodium acetate.

When tin or titanate compounds are used in the preparation of carboxylicacid terminated polyesters via reaction of diol with dicarboxylic acid,the level preferably is in the range of 0.0001 to 0.05 wt %.

When the group —R²— has structure VI with p of 1 or greater, thecompound having structure X is preferably made by one or more reactionof one or more dicarboxylic acid with one or more diol.

Embodiment (a) defined herein above is preferably made by reaction of adiepoxide with a dicarboxylic acid having the structure HOOC—R¹¹—COOH.Suitable and preferred —R¹¹— groups are the same as the suitable andpreferred —R³— groups.

Embodiment (b) defined herein above is preferably made by reaction of adiepoxide with a dicarboxylic acid that is a polyester (herein called“PEb1”). PEb1 is preferably made by reacting a single dicarboxylic acid(“DAb1”) with a single diol (“DOb1”). DAb1 has the structureHOOC—R¹²—COOH. Suitable and preferred —R¹²— groups are the same as thesuitable and preferred —R³— groups. DOb1 has the structure HOR¹³—OH,where —R¹³— has the structure VII. Suitable and preferred —R¹³— groupsare the same as those described for structure VII. A sufficient amountof DAb1 is used so that the reaction with DOb1 will produce a polyesterthat is a dicarboxylic acid.

Embodiment (c) defined herein above is preferably made by reaction of adiepoxide with a dicarboxylic acid that is a polyester (herein called“PEc1”). PEc1 is preferably made by reacting a single dicarboxylic acid(“DAc1”) with an intermediate polyester (“PEc2”). DAc1 has the structureHOOC—R¹³—COOH. Suitable and preferred —R¹³— groups are the same as thesuitable and preferred —R³— groups. PEc2 is preferably made by reactionof a dicarboxylic acid (“DAc2”) with one or more diol (“DOc1”). DAc2 hasthe structure HOOC—R¹⁴—COOH. Suitable and preferred —R¹⁴— groups are thesame as the suitable and preferred —R³— groups. Preferably DAc2 isdifferent from DAc1. DOc1 has the structure HOR¹⁵—OH, where —R¹⁵— hasthe structure VII. Relative amounts of DOc1 and DAc2 are used so that asignificant amount of the product PEc2 is formed that has one terminal—OH group and one terminal —COOH group.

Embodiment (d) defined herein above is preferably made by reaction of adiepoxide with a dicarboxylic acid that is a polyester (herein called“PEd1”). PEd1 is preferably made by reacting a single dicarboxylic acid(“DAd1”) with an intermediate polyester (“PEd2”). DAd1 has the structureHOOC—R¹⁶—COOH. Suitable and preferred groups are the same as thesuitable and preferred —R³— groups. PEd2 is preferably made by reactionof a dicarboxylic acid (“DAd2”) with one or more diol (“DOd1”). DAd2 hasthe structure HOOC—R¹⁷—COOH. Suitable and preferred —R¹⁷— groups are thesame as the suitable and preferred —R³— groups. Preferably DAd2 isdifferent from DAd1 . DOd1 has the structure HOR¹⁸—OH, where —R¹⁸— hasthe structure VII. Relative amounts of DOd1 and DAd2 are used so that asignificant amount of the product PEd2 is formed that has two terminal-OH groups.

Reactions between carboxylic acid groups and hydroxyl groups arepreferably conducted in the presence of one or more catalyst. Preferredcatalysts are tin compounds and titanate compounds. Among tin compounds,preferred are dibutyltins, tetrabutyltins, tin tetrachloride,dioctyltins, monobutyltins, and stannous tins; more preferred arehydroxybutyltin oxide, monobutyltin tris(2-ethylhexanoate), and stannous2-ethylhexanoate. Among titanate compounds, preferred aretetraalkyltitanates; more preferred are tetra(iso-propyl) titanate andtetra(n-butyl) titanate.

For reactions between carboxylic acid groups and hydroxyl groups, when acatalyst is present, the preferred amount is 0.0001% to 0.05% by weightbased on the sum of the weights of the compounds bearing carboxylic acidgroups plus the compounds bearing hydroxyl groups.

The composition of the present invention contains one or more epoxycuring agent. An epoxy curing agent is a compound in which each moleculecontains two or more active hydrogen atoms. An active hydrogen atom is ahydrogen atom that is capable of reacting with an epoxy terminatedcompound as follows:

where R²³— and R²⁴— are independently any chemical groups. The activehydrogen is the hydrogen atom attached to R²³— on the left hand side ofthe above chemical reaction. Preferably, R²³— has the structure R²⁵—Z—,where R²⁵— is a chemical group and —Z— is a divalent chemical group.Preferably, —Z— is

where R²⁶— is a chemical group. Preferably —Z— is XVI. Preferably, R²⁶—is either a hydrogen atom or a chemical group in which a carbon atom inR²⁶— is bonded to the nitrogen atom shown in XVI. When R²⁶— is nothydrogen, preferred R²⁶— groups are alkyl groups. It is considered thatwhen R²⁶— is a hydrogen atom, that hydrogen atom is an active hydrogenatom. Preferred active hydrogen atoms are part of a primary amino groupor a secondary amino group.

Preferred epoxy curing agents are selected from phenalkamines, Mannichbases, phenalkamides, amine terminated amide resins, aminoimidazoles,and mixtures thereof. More preferred are Mannich bases, amine-functionalamide resins, and mixtures thereof.

Preferred Mannich bases are reaction products of Mannich baseprecursors. Preferably, the Mannich base precursors comprise one or morephenol compound and one or more diamine As Mannich base precursors,preferred phenol compounds have the structure IX

where R¹⁹— is an aliphatic group. Preferably, R¹⁹— is an alkyl group;more preferably a branched alkyl group. Preferably, R¹⁹— has 7 or fewercarbon atoms; more preferably 6 or fewer carbon atoms; more preferably 5or fewer carbon atoms. Preferably, R¹⁹— has 2 or more carbon atoms; morepreferably 3 or more carbon atoms.

As Mannich base precursors, preferred diamines are selected fromstructure XII or structure XIII or a mixture thereof:

where —R²⁰— and —R²¹— and —R²²— are independently divalent organicgroups. Preferably, —R²⁰— is aliphatic; more preferably alkyl; morepreferably branched alkyl. Preferably, —R²⁰— has 15 or fewer carbonatoms; more preferably 12 or fewer carbon atoms; more preferably 10 orfewer carbon atoms. Preferably, —R²⁰— has 6 or more carbon atoms; morepreferably 8 or more carbon atoms. Preferably, —R²¹— and —R²²— areidentical. Preferably, —R²¹— is alkyl. Preferably, —R²¹— has 4 or fewercarbon atoms; more preferably 1 carbon atom.

Preferred amine terminated amide resins are reaction products ofprecursors that include one or more dicarboxylic acid and one or morediamine For formation of amine terminated amide resins, preferreddicarboxylic acids are dimer acids, which are the reaction products oftwo molecules of unsaturated fatty acid. Unsaturated fatty acids havethe structure R²⁵—COOH, where R²⁵— is an aliphatic group having eight ormore carbon atoms one or more carbon-carbon double bond. Preferably,R²⁵— has 12 or more carbon atoms. For formation of amine terminatedamide resins, preferred diamines are ethylenediamine,diethylenetriamine, triethylenetriamine, tetraethylenepentamine,piperazine, aminoethylpiperazine, isophorone diamine, xylylenediamine,and mixtures thereof; more preferred are ethylenediamine,diethylenetriamine, triethylenetriamine, tetraethylenepentamine, andmixtures thereof.

Preferred epoxy curing agents have active hydrogen equivalent weight of30 or higher; more preferably 50 or higher. Preferred epoxy curingagents have active hydrogen equivalent weight of 150 or lower; morepreferably 100 or lower.

Preferred epoxy curing agents are liquid at 25° C. Preferably, epoxycuring agent has viscosity at 25° C. of 300 mPa·s (300 cps) or higher.Preferably, epoxy curing agent has viscosity at 25° C. of 55,000 mPa·s(55,000 cps) or lower; more preferably a viscosity at 25° C. of lessthan 20,000 mPa·s (20,000 cps). Viscosity is measured with a Brookfieldviscometer according to method ASTM D2196-10 (ASTM, West Conshohocken,Pa., USA).

Preferably, the epoxy curing agent has number-average molecular weightof 750 or higher. Preferably, the amount of epoxy curing agent that ispresent in the composition of the present invention and that hasmolecular weight of less than 500 is 25% or less, by weight based on thetotal weight of all epoxy curing agents present in the composition ofthe present invention.

The weight ratio of epoxy terminated polyester to epoxy curing agent ischaracterized herein as 100:X. Preferably, X is 2 or greater; morepreferably 4 or greater; more preferably 6 or greater. Preferably, X is100 or less; more preferably 75 or less; more preferably 50 or less.

An isocyanate compound is any compound the molecule of which containsthe group —NCO. Preferably, the composition of the present inventioneither contains no isocyanate compound or else, if any isocyanatecompound is present, the total amount of all isocyanate compounds is0.05% or less by weight based on the weight of the composition of thepresent invention.

The compositions of the present invention may be used for a wide varietyof purposes. Preferably, a composition of the present invention is usedas an adhesive composition that is used to bond a first substrate to asecond substrate. Preferably, one or more epoxy terminated polyester ismixed with one or more epoxy curing agent and optionally with a solvent;the mixture is applied to a first substrate to form a layer on the firstsubstrate; solvent (if present) is evaporated or allowed to evaporate; asecond substrate is brought into contact with the layer of the mixture;and the mixture is cured or allowed to cure.

Preferably, when the epoxy terminated polyester is mixed with epoxycuring agent, the resulting mixture is a liquid having viscosity of25,000 mPa·s (25,000 cps) or less at 25° C. The individual components(epoxy terminated polyester and epoxy curing agent) are heatedindividually and then mixed with a static mixer and applied to thecoating head/station and maintained at the set application temperatureduring the coating process. The solventless epoxy adhesive should becapable of being applied at an application temperature of 40° C. to 60°C. but may be useful at temperatures ranging as high as 75° C. The useof elevated application temperature permits the reduction of applicationviscosity; the usable application viscosity at elevated temperature issummarized for use at temperatures of 40° C. and 50° C. but is notlimited by these operating parameters. Preferably, the resulting mixtureis a liquid having viscosity of 10,000 mPa·s (10,000 cps) or less at 40°C.; more preferably 6,000 mPa·s (6,000 cps) or less at 40° C.Preferably, the resulting mixture is a liquid having viscosity of 8,000mPa·s (8,000 cps) or less at 50° C.; more preferably 5,000 mPa·s (5,000cps) or less at 50° C.

A composition is considered herein to cure if the viscosity increases.Preferably, when the epoxy terminated polyester is mixed with epoxycuring agent at 25° C., the viscosity of the resulting mixture increasesby a factor of 5 or more at 25° C. in 500 minutes or less; morepreferably in 200 minutes or less. Preferably, when the epoxy terminatedpolyester is mixed with epoxy curing agent at 40° C., the viscosity ofthe resulting mixture increases by a factor of 20 or more at 40° C. in200 minutes or less; more preferably in 100 minutes or less.

Preferred substrates are polymer films, metalized polymer films, metalfoils, polymer-backed metal foils, ceramic coated polymer films, andcombinations thereof.

The following are examples of the present invention.

Abbreviations used below are as follows:

-   AV=Acid Value, measured by the method of ASTM D3644-06 (American    Society for testing and Materials, Conshohocken, Pa., USA).-   OHN=Hydroxyl Number, measured by the method of ASTM E1899-08.-   Amine Value=measured by the method ASTM D2074-07 for Test Methods    for Total, Primary, Secondary, and Tertiary Amine Values of Fatty    Amines by Alternative Indicator Method.-   Visc.=Viscosity, which is measured by employing a Brookfield RV    DV-II+Viscometer with a thermostated small sample adapter with a    spindle #27 and varying the temperature over a range of 25 to 70° C.    in increments of 5° C. and allowing the sample to stabilize at    temperature for 20 to 30 mins prior to recording viscosity.    Viscosity is reported in milliPascal·seconds (mP·s), which is equal    to centipoise.-   PO-DE1=reaction product of dipropylene oxide and epichlorhydrin,    containing a mixture of products including the following:

-   PO-DE2=reaction product of dipropylene oxide and epichlorhydrin,    containing a mixture of products including the following:

-   The DER 736, from Dow Chemcial, has the flowing properties: EEW is    182.9, (SEC Analysis Mn 500, Mw 600, Mz 800, Polydispersity 1.2, Wt    Fraction ≦500 Dalton 44.6%, Wt. Fraction ≦1000 Daltons 92.0%.)-   Fascat™ 9100=hydroxybutyltin oxide, from Arkema, Inc., commercial    grade-   Unidyme™ 22=dimerized fatty acid, from Arizona Chemical, AV=192.9.-   Cardolite™ NC-541LV=phenalkamine curing agent, from Cardolite    Corporation.; Amine Value is 340, Active Hydrogen Equivalent is 125.-   Polypox™ HO15=Mannich base curing agent, from The Dow Chemical    Company; Amine Value of 375; Active Hydrogen Equivalent is 75.-   Polypox™ P370=polyaminoimidazoline hardener for epoxy resins, from    The Dow Chemical Company; Amine Value of 485; Active Hydrogen    Equivalent is 95.-   Epikure™ 3140=polyamide curing agent, reaction product of dimerized    fatty acid and polyamines, from Momentive; Amine Value of 375;    Active Hydrogen Equivalent of 95.-   Coex PP (75SLP)=Exxon Mobil Bicor SLP Oriented Polypropylene,    Non-Heat Sealable, thickness 19 micrometers (0.75 mils).-   Coex PP (70SPW)=Exxon Mobil Bicor SPW Coextruded Polypropylene,    thickness 18 micrometers (0.70 mils).-   PET=DuPont, Polyester, Poly(ethylene glycol—terephthalate),    thickness 23 micrometer (92 Gauge) thick polyester film.-   PE (GF-19)=Berry Plastics Corp., High slip low density polyethylene    film, thickness 25.4 micrometers (1.0 mil).-   Nylon=Honeywell Capran Emblem 1500, Biaxially Oriented Nylon 6 Film,    thickness 15 micrometers.-   PET-Met=FILMTech Inc., Metallized Polyester film, thickness 25.4    micrometers.-   OPP-Met=AET Films, Metallized Oriented Polypropylene Film, MT Film,    Heat Sealable, thickness 18 micrometers.-   Backed Foil=12 micrometer (48 Gauge) Polyester (PET) Film laminated    to 0.00035 mil Al Foil with Adcote 550/Coreactant F at 3.26 g/m²    (2.00 lbs/ream).-   PET (92LBT)=DuPont, Polyester, Poly(ethylene glycol—terephthalate),    thickness 23 micron (92 Gauge).-   Mn=number-average molecular weight-   Mw=weight-average molecular weight-   EEW=epoxy equivalent weight, which is the mass per mole of epoxy    groups-   Active Hydrogen Equivalent=mass per mole of active hydrogens; an    active hydrogen is a hydrogen atom attached to the nitrogen atom of    an amine group.

EXAMPLE 1 Preparation of Epoxy Resin 1

Item Monomer/Intermediate Charge 1 Isophthalic Acid 1023.35 2 DiethyleneGlycol 572.30 3 Ethylene Glycol 315.60 4 Fascat 9100 (Hydroxybutyltinoxide) 0.5842 5 Adipic Acid 1349.81

Charged Items 1-4 to vessel at Ambient Temperature (25-30° C.). Heatedresin to 100° C. under Nitrogen with stirring. Heated resin to 225° C.and hold at 225° C., When ca.50% of theoretical water was off. MonitoredAV and In-Process Viscosity. Maintained at 225° C. until AV<ca. 80.Cooled Resin to <125° C. Added Item 5; Maintained at 125-135° C. for0.50 Hrs. Increased Temp to 225° C. and Maintained at 225° C. MonitoredAV and Visc; Maintained at 225° C. until AV<ca. 200. Cooled Resin toabout 150° C.; Filtered and Packaged. The final resin had the followingproperties: Acid Value (AV) 199, Mn 650, Mw 1250, Mz 2050, Wt.Fraction≦500 Daltons 22.3%, Wt. Fraction≦1000 Daltons 49.5%,Viscosity at24.5° C. of 515,000 mPa·s.

EXAMPLE 2 Polyester Preparation

Item Ingredient Charge (g) 1 Isophthalic Acid 451.50 2 Diethylene Glycol1081.30 3 Fascat 9100 (Hydroxybutyltin oxide) 0.5543 4 Adipic Acid1600.78

Charged Items 1-3 to vessel at Ambient Temperature (25-30° C.). Heatedresin to 100° C. under Nitrogen with stirring. Heated resin to 225° C.and held at 225° C., When ca.50% of theoretical water was off. MonitoredAV and In-Process Viscosity. Maintained at 225° C. until AV <ca. 75.Cooled Resin to <125° C. Add Item 4; Maintained at 125-135° C. for 0.50Hrs. Increased Temp to 225° C. and Maintained at 225° C.; Applied Vacuumat 400 mm as needed as to decrease AV to final target property.Monitored AV and Visc; Maintained at 225° C. until AV <ca. 155. CooledResin to about 150° C.; Filtered and Packaged. The final resin had thefollowing properties: Acid Value (AV) 149.73, Mn 950, Mw 1750, Mz 2550,Wt. Fraction ≦500 Daltons 10.6%, Wt. Fraction ≦1000 Daltons 32.1%,Viscosity at 25° C. of 29500 mPa·s.

EXAMPLE 3 Polyester Preparation

Item Ingredient Charge (g) 1 Isophthalic Acid 451.94 2 Diethylene Glycol567.80 3 Ethylene Glycol 316.34 4 Fascat 9100 (Hydroxybutyltin oxide)0.6028 5 Adipic Acid 1601.83

Charged Items 1-4 to vessel at Ambient Temperature (25-30° C.). Heatedresin to 100° C. under Nitrogen with stirring. Heated resin to 225° C.and hold at 225° C., When ca.50% of theoretical water was off. MonitoredAV and In-Process Viscosity. Maintained at 225° C. until AV <ca. 75.Cooled Resin to <125° C. Added Item 5; Maintained at 125-135° C. for0.50 Hrs. Increased Temp to 225° C. and Maintained at 225° C.; AppliedVacuum at 436 mm as needed as to decrease AV to final target property.Monitored AV and Visc; Maintained at 225° C. until AV <ca. 155. CooledResin to about 150° C.; Filtered and Packaged. The final resin had thefollowing properties: Acid Value (AV) 157, Mn 750, Mw 1500, Mz 2350, Wt.Fraction ≦500 Daltons 18.1%, Wt. Fraction ≦1000 Daltons 41.3%, Viscosityat 25° C. of 22,175 mPa·s.

EXAMPLE 4 Polyester Preparation

Item Ingredient Charge (g) 1 Isophthalic Acid 940.17 2 Diethylene Glycol572.60 3 Ethylene Glycol 316.00 4 Fascat 9100 (Hydroxybutyltin oxide)0.3169 5 Adipic Acid 1238.98

Charged Items 1-4 to vessel at Ambient Temperature (25-30° C.). Heatedresin to 100° C. under Nitrogen with stirring. Heated resin to 225° C.and hold at 225° C., When ca.50% of theoretical water was off. MonitoredAV and In-Process Viscosity. Maintained at 225° C. until AV <ca. 80.Cooled Resin to <125° C. Added Item 5; Maintained at 125-135° C. for0.50 Hrs. Increased Temp to 225° C. and Maintained at 225° C. MonitoredAV and Visc; Maintained at 225° C. until AV <ca. 165. Cooled Resin toabout 150° C.; Filtered and Packaged. The final resin had the followingproperties: Acid Value (AV) 169, Mn 950, Mw 2000, Mz 3250, Wt. Fraction≦500 Daltons 12.5%, Wt. Fraction ≦1000 Daltons 31.0%, Viscosity at 25°C. of 221,750 mPa·s.

EXAMPLE 5 Polyester Preparation

Item Ingredient Charge (g) 1 Isophthalic Acid 908.62 2 Diethylene Glycol1126.80 3 Fascat 9100 (Hydroxybutyltin oxide) 0.5730 4 Adipic Acid1198.87

Charged Items 1-3 to vessel at Ambient Temperature (25-30° C.). Heatedresin to 100° C. under Nitrogen with stirring. Heated resin to 225° C.and hold at 225° C., When ca.50% of theoretical water was off. MonitoredAV and In-Process Viscosity. Maintained at 225° C. until AV <ca. 75.Cooled Resin to <125° C. Added Item 4; Maintained at 125-135° C. for0.50 Hrs. Increased Temp to 225° C. and Maintained at 225° C.; AppliedVacuum at 394 mm as needed as to decrease AV to final target property.Monitored AV and Visc; Maintained at 225° C. until AV <ca. 135. CooledResin to about 150° C.; Filtered and Packaged. The final resin had thefollowing properties: Acid Value (AV) 158, Mn 1150, Mw 2350, Mz 3750,Wt. Fraction ≦500 Daltons 8.5%, Wt. Fraction ≦1000 Daltons 23.6%,Viscosity at 25° C. of 175,000 mPa·s.

EXAMPLE 6 Polyester Preparation

Item Ingredient Charge (g) 1 Isophthalic Acid 942.70 2 Diethylene Glycol654.60 3 Ethylene Glycol 362.20 4 Fascat 9100 (Hydroxybutyltin oxide)0.3168 5 Adipic Acid 1239.19

Charged Items 1-4 to vessel at Ambient Temperature (25-30° C.). Heatedresin to 100° C. under Nitrogen with stirring. Heated resin to 225° C.and hold at 225° C., When ca.50% of theoretical water was off. MonitoredAV and In-Process Viscosity. Maintained at 225° C. until AV <ca. 80.Cooled Resin to <125° C. Added Item 5; Maintained at 125-135° C. for0.50 Hrs. Increased Temp to 225° C. and Maintained at 225° C.; AppliedVacuum at 327 mm as needed as to decrease AV to final target property.Monitored AV and Visc; Maintained at 225° C. until AV <ca. 105. CooledResin to about 150° C.; Filtered and Packaged. The final resin had thefollowing properties: Acid Value (AV) 98, Mn 1200, Mw 2450, Mz 3900, Wt.Fraction ≦500 Daltons 7.6%, Wt. Fraction ≦1000 Daltons 22.2%, Viscosityat 25° C. of 271,500 mPa·s.

EXAMPLE 7 Polyester Preparation

Item Ingredient Charge (g) 1 Isophthalic Acid 1158.60 2 DiethyleneGlycol 720.90 3 Ethylene Glycol 398.30 4 Fascat 9100 (Hydroxybutyltinoxide) 0.4089 5 Adipic Acid 1525.85

Charged Items 1-4 to vessel at Ambient Temperature (25-30° C.). Heatedresin to 100° C. under Nitrogen with stirring. Heated resin to 225° C.and hold at 225° C., When ca.50% of theoretical water was off. MonitoredAV and In-Process Viscosity. Maintained at 225° C. until AV <ca. 80.Cooled Resin to <125° C. Added Item 5; Maintained at 125-135° C. for0.50 Hrs. Increased Temp to 225° C. and Maintained at 225° C.; AppliedVacuum at 435 mm as needed as to decrease AV to final target property.Monitored AV and Visc; Maintained at 225° C. until AV <ca. 160. CooledResin to about 150° C.; Filtered and Packaged. The final resin had thefollowing properties: Acid Value (AV) 153, Mn 650, Mw 1550, Mz 2650, Wt.Fraction ≦500 Daltons 19.2%, Wt. Fraction ≦1000 Daltons 42.8%, Viscosityat 25° C. of 173,750 mPa·s.

EXAMPLES 8-26 Preparations of Epoxide Terminated Polyester Resins

The preparations in Examples 8-26 were similar. Diepoxide, one or morediacid, and catalyst were charged to the reactor. Slowly Heated to135-140° C. Maintained at 135-140° C. for ca. 0.50 Hrs and then heatedto 150-155° C. and maintained at 150-155° C. for ca. 1.5 to 2 Hrs andthen monitored AV and Viscosity. Maintained at 150-155° C. and monitoredAV and Visc until AV <1.0. Transferred Resin and Package.

TABLE 1 Example Number: 8 9 10 11 12 13 14 Ingredient (g) DER 736 425.36426.94 600.93 503.22 1593.93 1900.35 1900.42 Isophthalic Acid 92.9293.00 348.83 333.00 299.80 Adipic Acid 114.00 29.24 Polyester Resin ofEx. 1 373.19 EthylTriphenyl- 0.2486 0.2575 0.3061 0.3640 0.9532 0.75900.4035 phosphonium Iodide Properties EEW 544.71 482.29 472.88 771.14487.37 416.73 411.51 Acid Value 0.11 ≦0.05 ≦0.05 ≦0.05 0.1 0.09 0.07 Mn1000 550 1200 1950 1400 1150 1050 Mw 3800 1400 3100 4400 4400 3750 3850Mz 9600 2850 6350 7600 10500 9500 10350 Wt. Fraction ≦500 (%) 16.8 28.813.0 4.8 10.1 15.6 17.4 Wt. Fraction ≦1000 (%) 28.0 54.2 24.2 11.1 20.927.6 28.9 Viscosity at 25° C. (mPa*s) 18425 16300 3850 30400 18500 50256100 Viscosity at 70° C. (mPa*s) 535.0 467.5 345.0(a) 1665.0(a) 900.0(a)365.0(a) 430.0(a) (a)Viscosity at 60° C.

TABLE 2 Example Number: 15 16 17 18 19 20 Ingredient (g) DER 736 1953.001041.90 1002.17 1008.19 784.08 792.79 Isophthalic Acid 427.40 PolyesterResin of Ex. 2 839.04 770.69 Polyester Resin of Ex. 3 753.53 PolyesterResin of Ex. 4 655.66 Polyester Resin of Ex. 5 780.42EthylTriphenylphosphonium 1.4638 0.5199 0.5067 IodideBenzyltrimethylammonium 0.5630 Chloride Sodium Carbonate 0.5571 SodiumAcetate 0.5346 Properties EEW 482.29 492.53 598.00 634.90 802.95 694.54Acid Value 0.04 0.04 0.06 0.05 0.04 0.03 Mn 1600 1500 1550 1550 21002000 Mw 5500 4750 4800 4700 13400 10100 Mz 14050 9000 8950 8700 4450026900 Wt. Fraction ≦500 (%) 7.5 10.9 10.5 10.4 6.9 7.6 Wt. Fraction≦1000 (%) 20.1 19.2 17.1 17.6 13.2 15.1 Viscosity at 25° C. (mPa*s)18325 6512 6100 6000 23025 21800 Viscosity at 70° C. (mPa*s) 700.0(a)320.0 342.5 345.0 1025 890.0 (a)Viscosity at 65° C.

TABLE 3 Example Number: 21 22 23 24 25 26 Ingredient (g) DER 736 775.25763.54 679.89 600.32 1021.77 738.40 Polyester Resin of Ex. 4 520.90Polyester Resin of Ex. 5 917.33 Polyester Resin of Ex. 6 923.08 1010.75Polyester Resin of Ex. 7 762.94 918.60 Sodium Acetate 0.5677 0.54670.3591 0.5156 0.5338 0.5217 Properties EEW 847.66 759.98 656.16 1244.17665.79 1417.64 Acid Value 0.04 <0.1 <0.1 <0.1 <0.1 <0.1 Mn 2150 17001400 3200 850 3050 Mw 13250 10000 7600 23450 5550 48200 Mz 39550 3150023000 82350 17150 248300 Wt. Fraction ≦500 (%) 6.5 9.6 12.0 3.4 19.5 3.6Wt. Fraction ≦1000 (%) 12.2 15.6 20.4 8.0 28.4 8.3 Viscosity at 25° C.(mPa*s) 58125 38550 21875 272500 13275 776667 Viscosity at 70° C.(mPa*s) 1862 1328 805.0 6150 565.0 15000

EXAMPLE 27 Preparation of Amine Curative

Item Monomer/Intermediate Charge 1 Unidyme 22 435.94 2Aminoethylpiperazine 242.56

Charged Item 1 and 2 to reactor, slowly heated to 200° C. Maintained at200° C. for 2 Hr; monitor water evolution, the final resin istransferred and packaged. The final resin had the following properties:Amine Value of 217.15, Viscosity at 25° C. of 51100 mPa·s.

EXAMPLE 28 Preparation of Amine Curative

Item Monomer/Intermediate Charge 1 Amine Curative of Example 6 200.84 2POLYPOX P370 70.01

Charged Item 1 and 2 to reactor, slowly heated to 50° C., maintain at50° C. for 4 Hrs. The resin is transferred and packaged. The final resinhad the following properties: Amine Value of 185.58, Viscosity at 25° C.of 10488 mPa·s.

EXAMPLE 29 Preparation of Amine Curative

Item Monomer/Intermediate Charge 1 Epikure 3140 252.23 2 POLYPOX P37084.35

Charged Item 1 and 2 to reactor, slowly heated to 50° C., maintain at50° C. for 4 Hrs. The resin is transferred and packaged. The final resinhad the following properties: Amine Value of 377.45, Viscosity at 25° C.of 4825 mPa·s.

EXAMPLE 30 Preparation of Amine Curative

Item Ingredient Charge (g) 1 Unidyme 22 877.12 2 Aminoethylpiperazine488.24

Charged Item 1 and 2 to reactor, slowly heated to 200° C. Maintained at200° C. for 2 Hr; monitor water evolution, the final resin istransferred and packaged. The final resin had the following properties:Amine Value of 238.9, Viscosity at 25° C. of 49000 mPa·s.

EXAMPLE 31 Preparation of Amine Curative

Item Ingredient Charge (g) 1 Unidyme 22 810.77 2 Triethylenetetramine(TETA) 488.71

Charged Item 1 and 2 to reactor, slowly heated to 200° C. Maintained at200° C. for 2 Hr; monitor water evolution, the final resin istransferred and packaged. The final resin had the following properties:Amine Value 169.64, Viscosity at 25° C. 54625 mPa·s.

The adhesion properties of the polyester-polyols and polyols wereevaluated with Amine based resins using a series of laminateconstructions. These two part adhesive systems were evaluated via asolvent hand casting method and laminator.

The following abbreviations are used to describe test results: as:adhesive split; ftr: film tear; fstr: film stretch; fsl: film sliver;at: adhesive transfer; sec: secondary; zip: zippery bond; pmt: partialmetal transfer. Adhesion bond strengths were determined on a 15 mm widestrip of laminate on a Thwing-Albert Tensile Tester (Model QC-3A) with a50 Newton load cell at a 10.0 cm/min rate.

Examples 32-61 were performed as follows: An epoxy terminated polyesterwas mixed with a curing agent at the mix ratio shown below, in ethylacetate at 50% concentration by weight. The solution was coated on afirst substrate to yield a dry coating weight of 1.6276 g/m² (1.0lb/ream). A second substrate was applied to the dried coating and theresulting laminate was cured at room temperature (approximately 25° C.).The bond strength was examined as a function of curing time and isreported below. The “Mix ratio” is the weight ratio of epoxy resin tocuring agent, expressed as 100:X. In the column labeled “laminatestructure,” the first substrate is listed, followed by the secondsubstrate.

As an example, in the table below, Example number 32 was a mixture ofepoxy resin made in Example 8, mixed with curing agent POLYPDX H015, ata weight ratio of epoxy resin to curing agent of 100:13.8. The bondstrength on substrates CoexPP (75SLP)/CoexPP (70SPW) at 7 days was 3.19Newton for a width of 15 mm, and the failure mode was film tear

TABLE 4 Example Number 32 33 34 Epoxy Resin from Ex. No. 8 8 9 Curingagent POLYPOX H015 Epikure 3140 Curing Agent Ex. 27 Mix Ratio 100:13.8100:17.4 100:45.0 Bond Strength (N/15 mm) Laminate Structure 7 Days 14Days 7 Days 14 Days 7 Days 14 Days CoexPP (75SLP)/CoexPP (70SPW) 3.19,ftr 2.05, ftr 2.26, ftr 2.02, ftr 4.84, ftr 3.83, ftr CoexPP (75SLP)/PE(GF-19) 1.65, as 1.75, as 1.16, as 2.76, ftr 6.54, ftr 6.00, ftr PET/PE(GF-19) 2.09, as 1.85, as 1.39, as 1.67, as 2.46, as 3.55, as Nylon/PE(GF-19) 1.39, as 1.81, as 1.66, as 1.39, as 6.49, ftr 5.29, ftrPET-Met/PE (GF-19) 1.26, as 1.35, as 1.18, as 1.19, as 2.59, ftr 2.90,ftr OPP-Met/PE (GF-19) 1.96, as 2.06, as 2.88, as 3.55, ftr 4.16, as4.58, as OPP-Met/CoexPP (70SPW) 1.85, as 2.10, as 2.49, as 2.08, ftr1.34, as 2.61, ftr Backed Foil/Nylon 0.50, at, sec 0.70, at, sec 0.16,as 0.21, as 1.99, as 0.70, as Backed Foil/PET (92LBT) 0.69, at, sec0.83, at, sec 0.22, as 0.22, as 2.21, as 2.42, as Backed Foil/PE (GF-19)1.02, at, sec 1.07, at, sec 0.96, as 0.68, as 2.98, as 2.95, as

TABLE 5 Example Number 35 36 37 Epoxy Resin from Ex. No. 9 9 10 Curingagent POLYPOX P370 Curing Agent Ex. 28 Curing Agent Ex. 28 Mix Ratio100:20.0 100:38.5 100:39.2 Bond Strength (N/15 mm) Laminate Structure 7Days 14 Days 7 Days 14 Days 7 Days 14 Days CoexPP (75SLP)/CoexPP (70SPW)2.22, ftr 2.59, ftr 2.42, ftr 2.76, ftr 2.58, ftr 1.73, ftr CoexPP(75SLP)/PE (GF-19) 2.66, ftr 2.89, ftr 3.39, ftr 3.23, ftr 4.84, ftr3.43, ftr PET/PE (GF-19) 2.38, as 2.36, as 2.73, as 2.30, as 1.40, as2.00, as Nylon/PE (GF-19) 2.81, ftr 3.09, ftr 3.95, ftr 2.98, ftr 2.13,as 2.16, as PET-Met/PE (GF-19) 1.17, as 1.85, as 2.46, as 1.90, ftr1.25, as 1.22, as OPP-Met/PE (GF-19) 1.21, as 2.03, as 2.57, as 3.08, as2.95, as 3.46, as OPP-Met/CoexPP (70SPW) 1.14, as 1.21, as 2.47, as2.32, ftr 1.43, as 1.73, as Backed Foil/Nylon 0.25, as 0.00, as 0.94, as0.56, as 0.46, as 0.09, as Backed Foil/PET (92LBT) 0.15, as 0.00, as0.97, as 0.36, as 0.28, as 0.16, as Backed Foil/PE (GF-19) 0.42, as0.57, as 2.30, as 2.23, as 0.78, as 1.12, as

TABLE 6 Example Number 38 39 40 Epoxy Resin from Ex. No. 10 11 11 Curingagent Curing Agent Ex. 27 Curing Agent Ex. 28 Curing Agent Ex. 27 MixRatio 100:45.9 100:24.1 100:28.2 Bond Strength (N/15 mm) LaminateStructure 7 Days 14 Days 7 Days 14 Days 7 Days 14 Days CoexPP(75SLP)/CoexPP (70SPW) 2.45, ftr 1.82, ftr 2.38, as 2.52, ftr 2.37, as2.11, as CoexPP (75SLP)/PE (GF-19) 3.11, as 3.29, ftr 2.34, as 2.17, as2.17, as 2.00, as PET/PE (GF-19) 2.18, as 2.35, as 3.31, as 2.63, as2.19, as 2.76, as Nylon/PE (GF-19) 1.72, as 2.23, as 2.28, as 2.59, as3.63, as 2.86, as PET-Met/PE (GF-19) 1.37, as 1.30, as 1.59, as 2.29, as4.40, as 3.82, as OPP-Met/PE (GF-19) 2.42, as 3.11, as 2.50, as 3.00, as2.25, as 3.06, as OPP-Met/CoexPP (70SPW) 2.88, as 2.86, as 2.20, as2.56, as 2.75, as 1.80, as Backed Foil/Nylon 1.23, as 1.29, as 0.00, as0.71, as 1.06, as 0.61, as Backed Foil/PET (92LBT) 0.52, as 1.21, as1.31, as 0.97, as 1.27, as 1.23, as Backed Foil/PE (GF-19) 1.20, as1.46, as 2.18, as 1.75, as 2.34, as 2.11, as

TABLE 7 Example Number 41 42 43 Epoxy Resin from Ex. No. 13 13 16 Curingagent Epikure 3140 Curing Agent Ex 27 Curing Agent Ex 30 Mix Ratio100:22.8 100:22.8 100:48.4 Bond Strength (N/15 mm) Laminate Structure 7Days 14 Days 7 Days 14 Days 7 Days 14 Days CoexPP (75SLP)/CoexPP (70SPW)3.11, ftr 3.59, ftr 1.52, as 2.37, ftr 1.88, ftr 2.27, ftr CoexPP(75SLP)/PE (GF-19) 2.23, as 2.46, as 1.93, as 1.99, as 3.52, as 2.99, asPET/PE (GF-19) 2.08, as 3.02, as 2.17, as 2.31, as 2.84, as 3.51, asNylon/PE (GF-19) 1.39, as 1.64, as 1.54, as 1.45, as 4.97, as 1.92, asPET-Met/PE (GF-19) 0.38, as 0.40, as 2.12, as 0.25, as 0.87, as 1.33, asOPP-Met/PE (GF-19) 0.52, as 0.57, as 0.68, as 0.38, as 1.06, as 1.18, asOPP-Met/CoexPP (70SPW) 0.48, as 0.70, as 1.09, as 0.38, as 1.12, as0.97, as Backed Foil/Nylon 0.83, as 0.69, as 0.91, as 0.46, as 1.89, as1.62, as Backed Foil/PET (92LBT) 0.36, as 0.37, as 0.93, as 0.25, as1.51, as 1.91, as Backed Foil/PE (GF-19) 1.33, as 1.92, as 1.72, as1.65, as 2.51, as 2.05, as

TABLE 8 Example Number 44 45 46 Epoxy Resin from Ex. No. 16 17 17 Curingagent Curing Agent Ex 31 Curing Agent Ex 30 Curing Agent Ex 31 Mix Ratio100:34.4 100:39.9 100:28.4 Bond Strength (N/15 mm) Laminate Structure 7Days 14 Days 7 Days 14 Days 7 Days 14 Days CoexPP (75SLP)/CoexPP (70SPW)1.87, ftr 2.95, ftr 1.93, as 1.05, as 1.70, ftr 1.40, ftr CoexPP(75SLP)/PE (GF-19) 3.84, ftr 4.03, ftr 1.55, as 0.73, as 1.99, as 2.18,as PET/PE (GF-19) 1.24, as 0.91, as 1.67, as 1.64, as 1.36, as 1.52, asNylon/PE (GF-19) 1.65, as 1.71, as 1.36, as 1.37, as 0.31, as 1.40, asPET-Met/PE (GF-19) 0.43, as 0.33, as 0.97, as 1.17, as 0.40, as 0.61, asOPP-Met/PE (GF-19) 0.58, as 0.39, as 0.89, as 0.75, as 0.42, as 0.77, asOPP-Met/CoexPP (70SPW) 0.49, as 0.64, as 1.10, as 0.98, as 0.49, as0.42, as Backed Foil/Nylon 0.76, as 0.69, as 0.36, as 0.94, as 0.27, as0.32, as Backed Foil/PET (92LBT) 0.90, as 0.17, as 0.46, as 0.79, as0.26, as 0.22, as Backed Foil/PE (GF-19) 1.18, as 1.21, as 1.55, as1.89, as 0.77, as 1.31, as

TABLE 9 Example Number 47 48 49 Epoxy Resin from Ex. No. 18 18 19 Curingagent Curing Agent Ex 30 Curing Agent Ex 31 Curing Agent Ex 30 Mix Ratio100:37.6 100:26.7 100:29.7 Bond Strength (N/15 mm) Laminate Structure 7Days 14 Days 7 Days 14 Days 7 Days 14 Days CoexPP (75SLP)/CoexPP (70SPW)1.42, as 1.03, as 1.79, as 1.77, ftr 1.11, as 1.06, as CoexPP (75SLP)/PE(GF-19) 0.93, as 1.41, as 1.65, as 2.10, as 1.10, as 1.54, as PET/PE(GF-19) 1.34, as 1.60, as 1.59, as 1.41, as 1.84, as 1.74, as Nylon/PE(GF-19) 0.88, as 1.30, as 1.42, as 1.20, as 2.11, as 1.58, as PET-Met/PE(GF-19) 0.94, as 0.50, as 0.48, as 0.43, as 0.69, as 1.08, as OPP-Met/PE(GF-19) 0.29, as 0.37, as 0.38, as 0.59, as 0.80, as 0.72, asOPP-Met/CoexPP (70SPW) 0.41, as 0.62, as 0.48, as 0.46, as 0.87, as1.26, as Backed Foil/Nylon 1.18, as 1.85, as 0.66, as 0.79, as 1.13, as1.83, as Backed Foil/PET (92LBT) 0.68, as 1.17, as 0.64, as 0.73, as0.59, as 1.41, as Backed Foil/PE (GF-19) 0.81, as 0.98, as 1.05, as0.97, as 1.41, as 2.03, as

TABLE 10 Example Number 50 51 52 Epoxy Resin from Ex. No. 19 15 20Curing agent Curing Agent Ex 31 Curing Agent Ex 31 Curing Agent Ex 30Mix Ratio 100:21.1 100:35.2 100:34.3 Bond Strength (N/15 mm) LaminateStructure 7 Days 14 Days 7 Days 14 Days 7 Days 14 Days CoexPP(75SLP)/CoexPP (70SPW) 1.10, as 1.23, as 1.65, ftr 2.35, ftr 0.30, as0.30, as CoexPP (75SLP)/PE (GF-19) 2.13, ftr 1.54, as 3.09, ftr 2.06,ftr 0.42, as 0.42, as PET/PE (GF-19) 1.39, as 1.37, as 2.31, as 2.28, as0.37, as 0.37, as Nylon/PE (GF-19) 1.23, as 1.28, as 1.16, as 1.71, as0.23, as 0.23, as PET-Met/PE (GF-19) 0.54, as 0.71, as 0.25, as 0.33, as0.58, as 0.58, as OPP-Met/PE (GF-19) 0.79, as 0.86, as 0.48, as 0.54, as0.64, as 0.64, as OPP-Met/CoexPP (70SPW) 0.76, as 0.79, as 0.47, as0.57, as 0.35, as 0.35, as Backed Foil/Nylon 0.90, as 0.81, as 0.63, as0.60, as 0.76, as 0.76, as Backed Foil/PET (92LBT) 0.80, as 0.70, as0.35, as 0.33, as 0.52, as 0.52, as Backed Foil/PE (GF-19) 1.00, as1.06, as 0.85, as 1.22, as 0.90, as 0.90, as

TABLE 11 Example Number 53 54 55 Epoxy Resin from Ex. No. 20 22 22Curing agent Curing Agent Ex 31 Curing Agent Ex 30 Curing Agent Ex 31Mix Ratio 100:24.4 100:31.4 100:22.3 Bond Strength (N/15 mm) LaminateStructure 7 Days 14 Days 7 Days 14 Days 7 Days 14 Days CoexPP(75SLP)/CoexPP (70SPW) 0.94, as 2.29, ftr 0.52, as 0.82, as 0.92, as1.96, fsl CoexPP (75SLP)/PE (GF-19) 1.25, as 2.57, fsl 0.82, as 1.01, as1.15, as 1.82, as PET/PE (GF-19) 1.56, as 1.87, as 0.76, as 0.87, as1.11, as 1.45, as Nylon/PE (GF-19) 1.11, as 1.31, as 0.67, as 0.83, as0.86, as 1.46, as PET-Met/PE (GF-19) 0.29, as 0.29, as 0.72, as 0.62, as0.28, as 0.35, as OPP-Met/PE (GF-19) 0.52, as 0.47, as 0.92, as 0.80, as0.46, as 0.47, as OPP-Met/CoexPP (70SPW) 0.50, as 0.51, as 0.79, as0.80, as 0.49, as 0.54, as Backed Foil/Nylon 0.72, as 0.80, as 1.04, as1.08, as 0.86, as 0.90, as Backed Foil/PET (92LBT) 0.36, as 0.42, as1.05, as 1.23, as 0.53, as 0.52, as Backed Foil/PE (GF-19) 0.89, as0.91, as 0.94, as 0.85, as 0.87, as 1.05, as

TABLE 12 Example Number 56 57 58 Epoxy Resin from Ex. No. 23 23 25Curing agent Curing Agent Ex 30 Curing Agent Ex 31 Curing Agent Ex 30Mix Ratio 100:36.3 100:25.9 100:37.6 Bond Strength (N/15 mm) LaminateStructure 7 Days 14 Days 7 Days 14 Days 7 Days 14 Days CoexPP(75SLP)/CoexPP (70SPW) 1.26, as 1.14, as 1.09, as 2.06, fsl 0.54, as0.90, as CoexPP (75SLP)/PE (GF-19) 1.63, as 1.35, as 1.68, as 3.27, ftr1.49, as 1.70, as PET/PE (GF-19) 1.60, as 1.41, as 1.25, as 1.77, as1.19, as 0.72, as Nylon/PE (GF-19) 1.15, as 1.64, as 1.61, as 2.56, as1.17, as 1.19, as PET-Met/PE (GF-19) 0.50, as 0.61, as 0.25, as 0.36, as0.56, as 0.52, as OPP-Met/PE (GF-19) 0.71, as 0.76, as 0.44, as 0.49, as0.60, as 0.64, as OPP-Met/CoexPP (70SPW) 0.73, as 0.85, as 0.43, as0.51, as 0.69, as 0.51, as Backed Foil/Nylon 1.42, as 1.14, as 0.67, as0.79, as 0.83, as 1.14, as Backed Foil/PET (92LBT) 1.12, as 1.16, as0.31, as 0.44, as 0.52, as 0.80, as Backed Foil/PE (GF-19) 1.11, as1.12, as 0.85, as 1.10, as 0.94, as 1.03, as

TABLE 13 Example Number 59 60 61 Epoxy Resin from Ex. No. 25 15 15Curing agent Curing Agent Ex 31 PRIAMINE 1071 JEFFAMINE D400 Mix Ratio100:26.7 100:40.2 100:23.8 Bond Strength (N/15 mm) Laminate Structure 7Days 14 Days 7 Days 14 Days 7 Days 14 Days CoexPP (75SLP)/CoexPP (70SPW)1.46, ftr 2.28, ftr 1.87, ftr 2.91, ftr 1.13, as 0.89, as CoexPP(75SLP)/PE (GF-19) 1.13, as 1.33, as 2.62, ftr 2.56, ftr 1.36, as 2.07,as PET/PE (GF-19) 1.23, as 1.79, as 0.78, as 1.07, as 1.29, as 1.26, asNylon/PE (GF-19) 0.83, as 0.30, as 1.45, as 1.49, ftr 1.04, as 0.67, asPET-Met/PE (GF-19) 0.25, as 0.00, as 0.23, as 0.00, as 0.00, as 0.17, asOPP-Met/PE (GF-19) 0.41, as 0.22, as 0.51, as 0.22, as 0.00, as 0.27, asOPP-Met/CoexPP (70SPW) 0.41, as 0.42, as 0.39, as 0.24, as 0.38, as0.25, as Backed Foil/Nylon 0.49, as 0.66, as 0.00, as 0.00, as 0.00, as0.00, as Backed Foil/PET (92LBT) 0.00, as 0.00, as 0.00, as 0.00, as0.00, as 0.00, as Backed Foil/PE (GF-19) 0.78, as 0.75, as 0.74, as0.65, as 0.27, as 0.78, as

1. A two-part composition comprising A) an epoxy terminated polyesterhaving the structure

wherein R¹— is

G- is

j is 0 to 5, —R²— is a divalent organic group, —R²¹— is a divalent alkylgroup, and —R²²— is a divalent alkyl group, and B) one or more epoxycuring agent, each molecule of which comprises two or more activehydrogen atoms that are each capable of reacting with an epoxy group. 2.The composition of claim 1, wherein each of said active hydrogen atomsis part of a primary or secondary amine group.
 3. The composition ofclaim 1, wherein said curing agent is selected from the group consistingof phenalkamines, Mannich bases, phenalkamides, amine terminated amideresins, aminoimidazolines, and mixtures thereof.
 4. The composition ofclaim 1, wherein said curing agent has number-average molecular weightof 750 or greater, and wherein the amount of said curing agent havingmolecular weight of less than 500 is 25% or less by weight based on theweight of said curing agent.
 5. The composition of claim 1, wherein said—R²¹— has 3 carbon atoms and every —R²²— has 3 carbon atoms.
 6. Thecomposition of claim 5, wherein at least one —R²²— has the structureselected from


7. The composition of claim 1, wherein said —R²— is

wherein said —R³— and —R⁴— and —R⁵— is each independently a divalentorganic group, and wherein said p is 0 to
 20. 8. The composition ofclaim 7, wherein said —R³— is either —(CH₂)_(q)— or

wherein q is 1 to
 8. 9. The composition of claim 7, wherein said —R⁴— iseither —CH₂—CH₂— or —CH₂—CH₂—O—CH₂—CH₂—.